Motor fuel



Patented Dec. 3, 1935 UNITED sTATEs 7 M'o roa FUEL Nicolaas Max,Amsterdam, Netherlands, assignor, by mesne assignments, to ShellDevelopment Company, San Francisco, Calif., a corporation of Delaware NoDrawing. Application July 16, 1931, Serial No. I 551,297. In theNetherlands August 8, 1930 4 Claims."

My invention relates to a process for the manufacture of non-knockingfuels for internal combustion engines.

It is known that the so-calledknocking in the 5 motor cylinder can beavoided or reduced by admixing various substances with the motor fuel.By admixing these so-called antiknock agents it is possible toincrease'the highest useful compression of the gas mixture obtained fromthe fuel.

It has now been found that non-knocking fuels can be obtained by addingto a motor fuel, such as benzine, a small quantity of a metal compoundof the type cheaper than benzol for increasing the H. U. C. 15

R-;('J=QH X It has been found that the exhaust gases remain I free frompoisonous components. in which X represents an OH or NHz group, R. Inaddition to the above-mentioned metal com-' represents any organicradical, and R represents pounds other substances, such as halogencomeither hydrogen or a member of a cyclic radical pounds, which preventthe segregation of metal 20 of whichR forms-a part.- on the valves ofthe engine, and/or other anti- The metal compounds in question, ofwhich, knock agents may also be added to the motor fuel for instance,the copper'or the ferri compound at the same time.ofoxymethylene-camphor or the copper com- It is to be observed that theformula of the 5 pound of amino-methylene-acetone may be mencoppercompound of oxy-methylenecamphor is tioned, comply with the requirementsvery imobtained by substitutingthe H of the OH group portant forantiknock agents, of volatility and in two molecules ofoxy-methylenecamphor by a solubility in benzine and when added in veryCu, the formula thusbeing: V

CHP CH: H H 0112*- (3H:v HI oo-ou-o- =0 0 1 35 small quantities to thefuel have even an excep- In the case of amino-methyleneacetone tionalantiknock effect. CH:OO=0NH:

In addition to being readily volatile and readily l l I 40 soluble inbenzinethe metal salts of the oxy or H 7 amino-methylene compoundsmentioned have a t e metal co po is deriveddrom e B1101" characteristiccolour; for instance, ferrioxyform so that the formula is: methylenecamphor, even'in dilute solution, has

a very intensive reddish-violet colour.- I

It is evident from the following examples what (L H high satisfactoryresults are obtained with the a compounds in question: 1. To a standardbenzine having a H. U. C.' i 7' (highest useful compression) of 5.40sufficient R copper salt of oxymethylene camphor is added to l give theliquid a Cu content of 0.05%. As a result of this admixture the H. U.0., determined in the Ricardo engine, is increased to 5.72. When I somuch is added that the Cu. content of the liq- CHCC=CNH: uid becomes0.1%, the H. U. C. rises to 6.03. 55

2. To the same benzine as mentioned in Example 1 ferrisalt ofoxymethylene camphor is added until the liquid contains 0.025% Fe. It isfound that through this admixture the 'H. U. C. can be increased from5.40 to 5.64. 5

3. To a benzine with a-H. U. C. of 5.40 copper salt ofamino-methylene-acetone is added until the liquid contains 0.023% Cu. Itis then found that this increases the H. U. C. to 5.69.

From these examples it is clear that the metal compounds mentionedincrease the H. U. C. 'considerably.

. An important advantage of the metal compounds in question is that theyare considerably In these formulas the dotted lines represent complexvalences. Of course, another metal such as iron, nickel, cobalt and thelike may be used in place of copper.

It is to be noted that the present invention provides a process for themanufacture of nonknocking motor fuels comprising adding to a motor fuelof a relatively small quantity of r a metal compound of an organiccompound of the type RCC=CX t t 1'.

In this formula X represents an OH or NH: group, whilst R represents anyorganic radical, such as an alkylor aryl-group 'or the rest of a cyclicradical, of which both the carbon atom of the carbonyl group and thecarbon atom linked to the oxyor aminomethylene group form a part, thusbelonging to the type A satisfactory method of preparing oxymethylenecamphor and aminomethylene acetone and metal compound thereof is asfollows:

500 grams of alpha camphor are dissolved in 3 litres of toluol. Thesolution is heated to boiling point in a 5 litre-flask provided with areflux cooler of large diameter, and then '70 grams of sodium are slowlyadded. When the sodium has practically totally disappeared the boilingsolution is filtered and subsequently cooled with an ice-salt mixture.Then a quantity of amylformiate corresponding to the quantity ofcamphor, is added within 2 hours while vigorously shaking. The mixtureis slowly brought to room temperature and kept at that temperatureduring one night. An equal volume of iced water is then added and themixture shaken during minutes. All the Na-salt is thus dissolved in thewater layer. The aqueous layer is then separated from the toluol layer,the former layer being washed several times with ether or benzol inorder to eliminate all camphor and bomeol. The aqueous solution isfiltered, and the filtrate cooled at 0 C.. whereafter an excess of 30%acetic acid is added while vigorously shaking the flask.Oxymethylene-camphor precipitates in white crystalline particles, whichcan be very easily drained. The crystals 'are washed with water anddried. 158 grams of oxy-methylene-camphor are thus obtained, whichcorresponds to a yield of 54% based on the quantity of Na-camphor.

The copper compound of oxy-methylene camphor can be produced as follows:

36 grams of oxy-methylene camphor (0.2 mol.) are dissolved in 100 ccs.of 2n KOH while heating.

To this solution an excess of Cu SO4-S01llti0ll is.

added. The granular precipitate is drained, washed with water and driedduring 12 hours on a porous dish in vacuo over H2804. The product ispowdered and dissolved in benzol, and the solution is filtered in orderto eliminate impurities and evaporated on the water bath. The residue,which when powdered has a light green colour, is the Cucompound ofoxy-methylene camphor.

The ferric compound is prepared in a similar manner from oxy-methylenecamphor and FeCh in the presence of an excess of aqueous sodium acetatesolution.

Amino-methylene acetone can be prepared by shaking 29 grams of theNa-compound of oxymethylene acetone with 50 cos. of absolute alcohol and15 grams of pulverized NH4C1 during 12 hours, filtering the brownsolution from the salts, evaporating the alcohol and distilling theresidue in vacuo. Amino-methylene acetone passes over as a yellowish,oily liquid, which can be purified by redistillation.

' The copper compound of amino-methylene acetone is prepared in the samemanner as indicated above for that of oxy-methylene camphor.

Of course, other methods of preparing the foregoing compounds which aredescribed in the prior art, may be used.

What I claim is:

1. A gasoline type motor fuel containing a small amount sufllcient toimpart non-knocking properties to said fuel of a metal compound of anorganic compound of the type R-C=O 'CCHX in which the letter Xrepresents an OH or NH: group, the letter R represents anoxygen-substituted hydrocarbon radical, and the letter R representshydrogen or a member of the organic radical represented by the letter R.

2. A gasoline type motor fuel containing a smaJl amount of a heavy metalcompound of an organic compound of the type in which X represents onemember of the group consisting of 0H and NH2, R represents a hydrocarbonradical and R1 represents a member of the group consisting of hydrogenatom and a carbon atom of the radical R, said amount being sufficient toimprove the anti-knock rating of the fuel.

3. A gasoline type motor fuel containing a small amount of a heavy metalcompound of oxymethylene camphor, said amount being sufficient toimprove the anti-knock rating of the fuel.

4. A gasoline type motor fuel containing a small amount of a heavy metalcompound of aminomethylene acetone, said amount being sufficient toimprove the anti-knock rating of the fuel.

